Moulding compositions containing a mixture of a thermoplastic aromatic polycarbonate, a butadiene polymer and a copolymer based on ethylenically unsaturated monomers

ABSTRACT

Thermoplastic moulding compositions of 1. 70-30 % BY WEIGHT OF A THERMOPLASTIC, AROMATIC POLYCARBONATE AND 2. 30-70 % BY WEIGHT OF A MIXTURE OF 2.1. 10-40 PARTS BY WEIGHT OF A BUTADIENE POLYMER WITH BUTADIENE CONTENTS OF AT LEAST 5 % AND 2.2. 90-60 PARTS BY WEIGHT OF A COPOLYMER OF 2.2.1. 95-50 PARTS BY WEIGHT OF STYRENE, Alpha -METHYLSTYRENE, METHYLMETHACRYLATE OR MIXTURES THEREOF AND 2.2.2. 5-50 PARTS BY WEIGHT OF ACRYLONITRILE, METHACRYLONITRILE, METHYLMETHACRYLATE OR MIXTURES THEREOF, THE MOULDING COMPOSITIONS CONTAINING AT LEAST 5 % BY WEIGHT OF THE BUTADIENE POLYMER.

United States Patent [191 Margotte et al.

Inventors: Dieter Margotte, Krefeld;

Karl-Heinz Ott, Leverkusen; Hermann Schirmer, Krefeld; Giinther K'zimpf,KrefeldBockum; Giinter Peilstiicker, Krefeld-Bockum; Hugo Vernaleken,Krefeld-Bockum, all of Germany Bayer Aktiengesellschat't, Leverkusen,Germany Filed: Dec. 3, 1973 Appl. N0.: 421,488

Assignee:

Foreign Application Priority Data June 9, 1973 Germany 2329546 Oct. 25,1973 Germany 2353383 11.5. C1. 260/873 1m. c1. C08g 39/10 Field ofSearch 260/873, 47 XA, 94.7 R, 260/876 References Cited UNITED STATESPATENTS 4/1964 Grabowski 260/873 Mar. 25, 1975 3,162,695 12/1964Grabowski 260/873 3,239,582 3/1966 Keskkula et a1. 260/47 X 3,642,9462/1972 Grabowski 260/873 3,649,716 3/1972 Childers et al 260/8733,663,471 5/1972 Schirmer et a1. t. 260/873 3,742,088 6/1973 Holder eta1 260/873 Primary Examiner-Morris Liebman Assistant E.\'aminerT.Pertilla Attorney, Agent, or FirmConnolly and Hutz [57] ABSTRACTThermoplastic moulding compositions of 1. 7030 by weight of athermoplastic, aromatic polycarbonate and 2. 30-70 by weight of amixture of 2.1. 10-40 parts by weight of a butadiene polymer withbutadiene contents of at least 5 and 2.2. 90-60 parts by weight of acopolymer of 2.2.1. 95-50 parts by weight of styrene, a-methylstyrene,methylmethacrylate or mixtures thereof and 2.2.2. 5-50 parts by weightof acrylonitrile, methacrylonitrile, methylmethacrylate or mixturesthereof,

the moulding compositions containing at least 5 70 by weight of thebutadiene polymer.

5 Claims, No Drawings MOULDING COMPOSITIONS CONTAINING A MIXTURE OF ATHERMOPLASTIC AROMATIC POLYCARBONATE, A BUTADIENE POLYMER AND ACOPOLYMER BASED ON ETHYLENICALLY UNSATURATED MONOMERS This inventionrelates to thermoplastic moulding compositions composed of 1. 70-30% byweight of thermoplastic, aromatic polycarbonate and 2. 30-70% by weightof a mixture of 2.1. -40 parts by weight of a butadiene polymercontaining at least 5% of butadiene and 2.2. 90-60 parts by weight of acopolymer of 2.2.]. 95-50 parts by weight of styrene, a-methylstyrene,methylmethacrylate or mixtures thereof and a 2.2.2. 5-50 parts by weightof acrylonitrile, methacrylonitrile, methylmethacrylate or mixturesthereof, the said moulding compositions containing at least 5 by weightof the butadiene polymer.

The moulding compositions according to the invention may in principlecontain any thermoplastic polycarbonates. Polycarbonates are alreadyknown. They are generally prepared by reacting dihydroxy or polyhydroxycompounds with phosgene or diesters of carbonic acid.4,4'-Dihydroxy-diarylalkanes are particularly suitable dihydroxycompounds, including those which carry alkyl groups or chlorine orbromine atoms in the ortho-position to the hydroxyl group. The followingdihydroxy-diarylalkanes are preferred: 4,4-Dihydroxy-diphcnylpropane-2,2 (bisphenol A). tetramethyl-bisphenol A,tetrachloro-bisphenol A, tetrahromo-bisphenol A andbis-(4-hydroxyphenyl) -p-diisopropylbenzcnc. Branched polycarbonates arealso suitable. To prepare them, part of the dihydroxy compound, e.g. 0.2to 2 mols is replaced by a polyhydroxy compound. The following areexamples of suitable polyhydroxyl compounds: l,4-Bis-(4',4,2-dihydroxy-triphenyl-methyl)-benzene, phloro-glucinol,4.6-dimethyl-2,4,4-tri(4-hydroxyphenyl)-heptene-2;4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-benzene; l,-l,l-tri-(4-hydroxyphenyl)-ethane and 2,2-bis-[4,4-(4,4'-dihydroxydiphenyl)-cyclohexyl]propane.

Polycarbonates of this kind have been described in US. Pat. Nos.3,028,365; 2,999,835; 3,148,172; 3,271,368; 2,970,137; 2,991,273;3,271,367; 3,208,078; 3,014,891 and 2,999,846. Polycarbonates which havemolecular weights of 10,000 to 60,000 are preferred, and in particularthose with molecular weights of 20,000 to 40,000.

1n a preferred embodiment a mixture oftwo polycarbonates is used. Thismixture contains 50-85 by weight of a polycarbonate made from a halogenfree polyphenol and -50 by weight of a halogen containing polycarbonateof the formula Hal wherein n 15-200 1 X alkylene or alkylidene havingl-5 carbon atoms;

cycloalkylene or cyclolalkylidene having 5-15 carbon atoms; a singlebond; 0 or CH CH5 ('1 T ('3 i Q" CH3 ca Hal chlorine or bromine.

The final moulding compositions of this embodiment contain preferably 10to 30 by weight of the halogen containing polycarbonate.

As shown by the formula such halogen containing polycarbonates are basedon phenols containing at least two benzene nuclei and carrying 4 halogen(ch10- rine, bromine) atoms. The molecular weights of suchpolycarbonates are preferably from 16,000 to 35,000. When thesepolycarbonate mixtures are used the thermal stability and moduli ofelasticity found in the products are exceptionally high.

The butadiene polymers which are contained in the moulding compounds arepreferably copolymers of 5-95 by weight butadiene and 70-5% by weight ofstyrene, acrylonitrile, acrylic acid, methacrylic acid, C -C alkylesters of acrylic or methacrylic acid (methylmethacrylate isparticularly preferred), divinylbenzene and mixtures of thesecomonomers. Particularly suitable are the copolymers of 70-90% by weightof butadiene and 30-10% by weight of styrene; copolymers of -95% byweight of butadiene and 40-5% by weight of methylmethacrylate;copolymers of 30-95% by weight of butadiene and -570 by weight of butylacrylate; and copolymers of 60-80% by weight of butadiene and 40-20% byweight of acrylonitrile. These last mentioned copolymers may alsocontain small quantities (up to about 10%) of methacrylic acid and/ordivinylbenzene incorporated by polymerisation. Examples of terpolymersand quaterpolymers of the last mentioned kind are the copolymers of 63%of butadiene, 34% of acrylonitrile and 3% of methacrylic acid and thecopolymers of 60% by weight of butadiene, 36% by weight ofacrylonitrile, 3% of methacrylic acid and 1% of divinylbenzene.

The third compound of the moulding compositions according to theinvention consists of copolymers of 95-50 parts by weight of styrene,a-methylstyrene, methylmethacrylate or mixtures thereof and 5-50 partsby weight of acrylonitrile, methacrylonitrile, methylmethacrylate ormixtures thereof. Copolymers of this kind which are particularlypreferred are the products obtained from about to 60 by weight ofstyrene and 20-40 70 by weight of acrylonitrile as well as the analogouscopolymers obtained from a-methylstyrene.

The moulding compositions according to the invention can be obtained bymixing their components. According to a preferred method of producingthem, a latex of the butadiene polymer and a latex of the reslnouscopolymer are first mixed and the solids are precipitated from the mixedlatices and dried. The resulting mixture is then mixed with thepolycarbonate, eg in a double screw extruder.

According to a preferred embodiment of the invention, the butadienepolymer is present in the form of a network in the combined resinmatrix.

The moulding compositions of the invention are suitable for producingany kinds of moulded products, for example by injection moulding. It isparticularly advantageous in this moulding process that products with ahigh weld line strength are formed which can be used for complicatedmouldings. In addition, the moulding compositions of the invention haveexceptionally high dimensional stability when heated and are resistantto weathering. They are therefore particularly suitable for producingmouldings which are exposed to weathering.

EXAMPLES EXAMPLES 1-8 The following components were used for producingthe moulding compositions which were afterwards tested:

and parts by weight of a copolymer of 60 parts by weight of butadiene,36 by weight of acrylonitrile, 2 by weight of methacrylic acid and 2 byweight of divinylbenzene,

6. a mixture obtained by joint precipitation of the latices, of 70 partsby weight ofa copolymer of 72 by weight of styrene and 28 by weight ofacrylonitrile and parts by weight of a copolymer of 60 by weight ofbutadiene, 38 by weight of acrylonitrile and 2 by weight ofdivinylbenzene.

Products 1 and 2 were melted and extruded together and 3-6 were meltedand extruded together, using in both cases a double screw extruder attemperatures of 200260C. The higher the polycarbonate content of themixture, the higher were the operating temperatures employed within thegiven range.

The proportions in which the components were mixed and the physicalproperties determined in the moulding compounds are summarized in Table1.

Table 1 Example Example Example Example Example Example Example ExamplePolycarbonate 1) Parts by weight 40 40 40 Polycarbonate (2) do. 50Mixture (3) do. 60 50 40 30 50 Mixture (4) do. 6O Mixture (5) do. 6OMixture (6) do. 60 Butadiene polymer content of the composition 7! byweight 17.4 14.5 11.6 8.7 15 12 18 14.5 Elongation at break 7r (DIN53455) 35 52 90 34 26 43 45 Modulus of elasticity k /cm (DIN 53 455)17,700 18,600 19,700 21,200 20,000 19,800 17,700 21,000 Impact strengthcm kp cm (DIN 53 453) not broken Notched impact strength cm kp/cm (DIN53 453) 7 8 14 22 9 8 '12 6 WLS" cm kp/cm (based on DIN 53 453) 7 6 6 77 4 7 6 Vicat number (A) "C (DIN 53 460) 130 132 141 145 125 125 127 140Vicat number (B) "C (DIN 53 460) 108 I13 123 127 107 110 109 124"Wl.S=Wcld line strength was determined as follows: A small standardtest bar is produced by injccting the material from two opposite sidesso that a weld line is formed at the middle of the bar. The impactstrength of this moulding is determined by a method analogous to DIN 53453.

l. a polycarbonate of bisphenol A and phosgene having the relativeviscosity 1 1.30 (determined on a solution of 0.5 g of polycarbonate in100 ml of methylene chloride at 25C) and a molecular weight of M approx.30,000, a polycarbonate based on 94 mols of Bisphenol A and 6 mols 70 oftetrabromobisphenol A prepared by the known interface process and havinga relative viscosity of 11,- 1.28 and a molecular weight of M approx.28,000, a mixture obtained by a joint precipitation of the correspondinglatices of 71 parts by weight of a copolymer of by weight styrene and 20by weight of acrylonitrile and 29 parts by weight of a copolymer of 63by weight of butadiene, 34 by weight of acrylonitrile and 3 70 by weightof methacrylic acid, I 4. a mixture obtained by joint precipitation ofthe latices of 75 parts by weight of a copolymer of'72 7( by weight ofstyrene and 28 70 by weight of acrylonitrile and 25 parts by weight of acopolymer of 60 7! by weight of butadiene, 36 by weight ofacrylonitrile, 3 by weight of methacrylic acid and 1 by weight ofdivinylbenzene, 5. a mixture obtained by joint precipitation of thelatices of 80 parts by weight of a copolymer of 70 by weight of styreneand 30 70 by weight of acrylog the moulding compositions which EXAMPLES9-14 The following components were used for preparing are afterwardsstsqa a. a polycarbonate based on Bisphenol A prepared by the phaseinterface process and having a relative viscosity of 1 1.28 and anaverage molecular weight of M approx. 28,000,

a polycarbonate based on mols of Bisphenol A and 15 mols oftetrachlorobisphenol A prepared by the phase interface process andhaving a relative viscosity of 1 1.31 and a molecular weight of Mapprox. 31,000,

. a polycarbonate based on mols of Bisphenol A and 10 mols 7c oftetrabromobisphenol A prepared by the phase interface process and havingthe relative viscosity "111 1.30 and a molecular weight of M approx.31,000,

d. a mixture, prepared by mutual precipitation of the latices, of 70parts by weight of a copolymer of 70 by weight of styrene and 30 byweight of acrylonitrile having an instrinsic viscosity of 1;, 0.79(determined in DMF at 20C) and 30 parts by weight of a copolymer of 70%by weight of butadiene and 30 /r' by weight of styrene.

e. a mixture, obtained by mutual precipitation of the a mixture obtainedby mutual precipitation of the latices, of 60 parts by weight of acopolymer of 70% by weight of styrene and 30% by weight of acrylonitrilehaving an instrinsic viscosity of 1;,- 1.0 and 40 parts by weight of acopolymer of 80% by weight of butadiene and 20% by weight ofmethylmethacrylate.

6 D) High molecular tetrabromobisphenol-A- p ycarbonate 1 1,08

I M =ca. l6.000 E) High molecular tetrabromobisphenol-A- polycarbonate 1[,08

M 35.000 5 F) Copolycarbonate of 84 mol-% bisphenol A ca and [6 mol-%tetrachlorobisphenol A 1 1,27

' M ca. 31.000 G) High molecular tetrachlorobisphenol-A- polycarbonate11 1,12

2. Copolymer mixtures H. A mixture obtained by joint precipitation ofthe latices of 7l parts by weight of a copolymer of 80 by weight styreneand by weight acryloni- Products (a) to (c) on the one hand arehomogenised l5 il d 29 parts b w i ht f a copolymer f 63 and extrudedwith products (e) to (f) on the other hand by weight butadiene, 34 byweight acryloniat temperatures of between 240 and 300C in double trileand 3 by weight methacrylic acid; shaft screws. 1. a mixture obtainedbyjoint precipitation ofthe lati- The proportions in which thecomponents are mixed ces of 80 parts by weight of a copolymer of 70 andthe physical properties determined in the moulding 20 by weight styreneand 7: by weight acrylonitrile compositions are summarized in Table 2. Vand 20 parts by weight of a copolymer of 60 by Table 2 Example 9 Example10 Example ll Example 12 Example 13 Example 14 Polycarbonate (a) Partsweight 40 40 20 Polycarbonate (h) 0. Polycarbonate (c) do. 40 20 Mixture(d) do. 0 Mixture (e) do. 60 3O Mixture (f) do. 60 60 30 Butadienepolymer content of the composition 7 '71 by weight 18 2t 24 i5 24 22.5Elongation at break 7c (DIN 53 455) 40 76 40 70 Modulus of elasticitykp/cm (DIN 53 455) 18500 23000 l7l00 l9600 17000 18200 Impact strengthcm kp/cm (DIN 53 453) not broken not broken Notched impact strength cmkp/cm (DIN 53 453) 11 t8 8 l3 7 l0 WLS" (based on DIN 53 453) 10 7 9 7 88 Vicat Number A (DlN 53 460) C 131 I36 l33 126 130 Vicat Number B (DIN53 460) "C 114 l25 109 ll 1 110 111 "See under Table l M a 7 V V 7 WW"W7 7 i EXAMPLE 15 weight butadiene, 36 by weight acrylonitrile, 2

r I 7 polycarbonates by weight methacrylic acid and by weight ql arlbm ssa V .g g g (17M) ih g fi fi i 45 J. a mixture obtained byjointprecipitation of the latii a concemm Ion 0 g ecu ar ces of 70 parts byweight of a copolymer of 72 7: WfFlg l f a lii m lt o, by weight styreneand 28 by weight acrylonitrile 4 l A) Bisphenol A polycarbonate TM =13)and 30 parts by weight of a copolymer of 60 by fgo W b h M Mm =ca.31.000 weight butadiene, 38 by weight acrylonitrile and B)Copolycarbonate 0 mo 1 isp eno 7 c and 20 moi-7c tetrabromobisphenol A 125 l 50 f. i ft h dlvmylbeinzenfit b b h A M =ca. 30.500 The followingtable contains the mixtures of the in- C) Low molecular tetra romo ispenopolycarbonate 7M L03 vention which were made by mixing the componentsin M. ca. 4.500

nPrqs -r nd th ir ssluda a- Table Example polycarbonate A) polycarbonateB) polycarbonate C) polycarbonate D) polycarbonate E) polycarbonate F)polycarbonate G) mixture H) mixture l) mixture J) Vicat A "C Vicat B Cmodulus of elasticity kp/cm determined according to DIN 53 460determined according to DIN 53 455 We claim: 1. A thermoplastic mouldingcomposition comprising 1. 70-30% by weight of a thermoplastic aromaticpolycarbonate and 2, 3070% by weight of a mixture of a. 10-40 parts byweight of a butadiene polymer having a butadiene content of at least30%, the remainder being styrene, acrylonitrile. acrylic acid,methacrylic acid, a C C alkyl ester of acrylic acid, a C C alkyl esterof methacrylic acid, divinylbenzene or a mixture thereof and b. 90-60parts by weight of a copolymer of i. 9550 parts by weight of styrene,a-methyl styrene, methylmethacrylate or a mixture thereof and ii. -50parts by weight of acrylonitrile, methacrylonitrile. methylmethacrylateor a mixture thereof, said moulding composition containing at least 5%by weight of said butadiene polymer and said thermoplastic aromaticpolycarbonate being a mixture of (l) 50 85% by weight of a polycarbonatebased on a halogen-free phenol and (II) 15-50% by weight of ahalogen-containing polycarbonate of the formula Hal X Hal o 0 Hal Halwherein n is to 200, X is alkylene or alkylidene having 1 to 5 carbonatoms; cyloalkylene or cycloalkylidene having 5 to 15 carbon atoms; asingle bond; -0- or CH CH 'in claim 1 wherein the butadiene polymer is acopolymer of to 95 /0 by weight of butadiene and 70 to 5 by weight ofbutyl acrylate.

5. A thermoplastic moulding composition as claimed in claim 1 whereinthe butadiene polymer is a copolymer of 60 to 80 by weight of butadieneand 40 to 20 7r by weight of acrylonitrile.

I Disclaimer 3,873,641.Dieter Margotte, Krefeld; Karl-Heinz Ott,Leverkusen; Hermann Schirmer, Krefeld; Gunther Kampf Krefeld-Bockum;Gunter Peilstocker, Krefeld-Bockum; Hugo Vernaleken, Krefeld-Bockum,Germany. MOULDING COMPOSITIONS CONTAINING A MIXTURE OF A THERMOPLASTICAROMATIC POLYCARBONATE, A BU- TADIENE POLYMER AND A COPOLYMER BASED ONETHYLENICALLY UNSATURATED MONOMERS. Patent dated Mar. 25, 1975.Disclaimer filed May 17, 1983, by the assignee, BayerAktiengesellschaft.

Hereby enters this disclaimer to all claims of said patent.

[Ofiicial Gazette September 27, 1983.]

Disclaimer 3,873,641.Dieter Margotte, Krefeld; Karl-Heinz Ott,Leverkusen; Hermann Schirmer, Krefeld; Gunther Kampfi Krefeld-Bockum;Gunter Peilstocker, Krefe1d-Bockum; Hugo Vernaleken, Krefeld-Bockum,Germany. MOULDING COMPOSITIONS CONTAINING A MIXTURE OF A THERMOPLASTICAROMATIC POLYCARBONATE, A BU- TADIENE POLYMER AND A COPOLYMER BASED ONETHYLENICALLY UNSATURATED MONOMERS. Patent dated Mar. 25, 1975.Disclaimer filed May 17, 1983, by the assignee, BayerAktiengesellschaft.

Hereby enters this disclaimer to all claims of said patent.

[Official Gazette September 27, 1983.]

1. A THERMOPLASTIC MOULDING COMPOSITION COMPRISING
 1. 70-30% BY WEIGHTOF A THERMOPLASTIC AROMATIC POLYCARBONATE AND
 2. 30-70% BY WEIGHT OF AMIXTURE OF A. 10-40 PARTS BY WEIGHT OF A BUTADIENE POLYMER HAVING ABUTADIENE CONTENT OF AT LEAST 30%, THE REMAINDER BEING STYRENE,ACRYLONITRILE, ACRYLIC ACID, METHACRYLIC ACID, A C1-C6 ALKYL ESTER OFACRYLIC ACID, A C1-C6 ALKYL ESTER OF METHACRYLIC ACID, DIVINYLBENZENE ORA MIXTURE THEREOF AND B. 90-60 PARTS BY WEIGHT OF A COPOLYMER OF I.95-50 PARTS BY WEIGHT OF STYRENE, A-METHYLSTYRENE, METHYLMETHACRYLATE ORA MIXTURE THEREOF AND II. 5-50 PARTS BY WEIGHT OF ACRYLONITRILE,METHACRYLONITRILE, METHYLMETHACRYLATE OR A MIXTURE THEREOF, SAIDMOULDING COMPOSITION CONTAINING AT LEAST 5% BY WEIGHT OF SAID BUTADIENEPOLYMER AND SAID THERMOPLASTIC AROMATIC POLYCARBONATE BEING A MIXTURE OF(1) 50-85% BY WEIGHT OF A POLYCARBONATE BASED ON A HALOGEN-FREE PHENOLAND (II) 15-50% BY WEIGHT OF A HALOGEN-CONTAINING POLYCARBONATE 0F THEFORMULA
 2. 30-70% by weight of a mixture of a. 10-40 parts by weight ofa butadiene polymer having a butadiene content of at least 30%, theremainder being styrene, acrylonitrile, acrylic acid, methacrylic acid,a C1-C6 alkyl ester of acrylic acid, a C1-C6 alkyl ester of methacrylicacid, divinylbenzene or a mixture thereof and b. 90-60 parts by weightof a copolymer of i. 95-50 parts by weight of styrene, Alpha-methylstyrene, methylmethacrylate or a mixture thereof and ii. 5-50parts by weight of acrylonitrile, methacrylonitrile, methylmethacrylateor a mixture thereof, said moulding composition containing at least 5%by weight of said butadiene polymer and said thermoplastic aromaticpolycarbonate being a mixture of (I) 50-85% by weight of a polycarbonatebased on a halogen-free phenol and (II) 15-50% by weight of ahalogen-containing polycarbonate of the formula
 2. A thermoplasticmoulding composition as claimed in claim 1, in which the polycarbonatehas a molecular weight of from 10,000 to 60,000.
 3. A thermoplasticmoulding composition as claimed in claim 1 wherein the butadiene polymeris a copolymer of 70 to 90 % by weight of butadiene and 10 to 30 % byweight of styrene.
 4. A thermoplastic moulding composition as claimed inclaim 1 wherein the butadiene polymer is a copolymer of 30 to 95 % byweight of butadiene and 70 to 5 % by weight of butyl acrylate.
 5. Athermoplastic moulding composition as claimed in claim 1 wherein thebutadiene polymer is a copolymer of 60 to 80 % by weight of butadieneand 40 to 20 % by weight of acrylonitrile.